CN102667025A - A reinforced polymer composite - Google Patents

A reinforced polymer composite Download PDF

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Publication number
CN102667025A
CN102667025A CN2010800513430A CN201080051343A CN102667025A CN 102667025 A CN102667025 A CN 102667025A CN 2010800513430 A CN2010800513430 A CN 2010800513430A CN 201080051343 A CN201080051343 A CN 201080051343A CN 102667025 A CN102667025 A CN 102667025A
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layer
polymer composite
reinforced polymer
elongated metal
metal element
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CN102667025B (en
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T·贝克尔兰德特
A·里普莱
A·萨姆斯
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Bekaert NV SA
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Bekaert NV SA
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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C3/00—Structural elongated elements designed for load-supporting
    • E04C3/02—Joists; Girders, trusses, or trusslike structures, e.g. prefabricated; Lintels; Transoms; Braces
    • E04C3/28—Joists; Girders, trusses, or trusslike structures, e.g. prefabricated; Lintels; Transoms; Braces of materials not covered by groups E04C3/04 - E04C3/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/041—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with metal fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/01—Reinforcing elements of metal, e.g. with non-structural coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Architecture (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Ropes Or Cables (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A reinforced polymer composite comprises a matrix of thermoplastic material, and the matrix is reinforced by at least one elongated metal element. The elongated metal element before being embedded in the matrix is coated with at least a first layer and a second layer, and the first layer comprises an adhesion promoting layer, and the second layer comprises a polyolefin copolymerized or grafted with at least one monomer comprising an anhydride or a carboxylic acid functional group. The reinforced polymer composite further comprises wood particles with concentration of 0% to 95% by weight. It also relates to a method to manufacture the reinforced polymer composite.

Description

Reinforced polymer composite
Technical Field
The present invention relates to a reinforced polymer composite. It also relates to a method of making the reinforced polymer composite. It also relates to an elongated metal element for reinforcing said composite material.
Background
Reinforced polymer composites, especially Wood Polymer Composites (WPCs), are widely used in construction applications. WPC is a composite material comprising wood and a polymer. As a building application, reinforced polymer composites such as WPCs are used for residential wall panels, optically closed fencing, balcony flooring or garden sheds, and the like. It is not useful for load bearing applications in construction because it can creep and sag severely under heavy loads.
To increase the stiffness and creep resistance of the composite, steel wires or steel cords are embedded in the composite.
WO2004/083541 discloses a composite material comprising a matrix of a thermoplastic synthetic polymer material and wood particles or cellulose-containing particles and embedded with steel wires or steel cords. The steel or steel wire rope is used as a reinforcing element. A thin layer of modified polymer is applied to the wire or cord before embedding in the matrix. The modified polymer interacts with the matrix and the steel wire or steel cord. The modifying polymer may be polypropylene. A drawback is that the reinforcing element is very easy to pull out of the composite material. On the other hand, the steel or steel cord cannot be embedded firmly in the matrix because of the poor adhesion between the reinforcing elements and the matrix. The load-bearing structure is therefore unstable when reinforced with such a composite.
WO 2009/082350 discloses a polymer/natural fiber composite particle using a coupling agent to improve compatibility between the polymer and natural fiber. The coupling agent is selected from the group consisting of maleic anhydride, maleic anhydride modified polymers, compounds having monofunctional or polyfunctional reactive nitrogen groups, and silanes. Longer natural fibers than conventional wood chips and mill tailings are used to improve the reinforcement of the composite particles. The natural fiber is cotton, hemp, jute, flax, ramie, sisal or cellulose wood fiber. Due to the nature of natural fibers themselves, the composite particles are not hard enough for load bearing applications to bear weight and forces.
Disclosure of Invention
The object of the present invention is to overcome the drawbacks of the prior art.
It is also an object of the present invention to provide a reinforced polymer composite having good adhesion between the composite and its reinforcement. More specifically, it is an object of the present invention to provide a reinforced wood polymer composite.
It is another object of the present invention to provide a method for manufacturing the reinforced polymer composite, in particular a reinforced wood polymer composite.
It is a further object of the present invention to provide an elongated metal element for reinforcing said polymer composite, in particular for reinforcing wood polymer composites.
According to the invention, the reinforced polymer composite comprises a matrix of thermoplastic material, said matrix being reinforced with at least one elongated metal element. The elongated metal elements are coated with at least a first layer and a second layer prior to embedding in the matrix. The first layer comprises an adhesion promoting layer and the second layer comprises a polyolefin copolymerized or grafted with at least one monomer comprising an anhydride or carboxylic acid functional group.
The reinforced polymer composite further comprises wood particles in a concentration of 0wt% to 95 wt%. The concentration of wood particles is 0wt% to 95 wt%. Preferably, the concentration of wood particles is 20 to 80 wt%. More preferably, the concentration of wood particles is 35 to 80 wt%. Most preferably, the concentration of wood particles is 70 to 80 wt%. As used herein, "wt%" refers to weight percent, and the total weight is the weight of the reinforced polymer composite.
For good adhesion to the substrate, the elongated metal elements are coated with at least a first layer and a second layer before being embedded in the substrate. Due to these two layers, the elongated metal elements are firmly embedded in the matrix.
The first layer includes an adhesion promoting layer such as a silicon-based coating, a titanium-based coating, or a zirconium-based coating.
According to the invention, "silicon-based coating" refers to any coating comprising silicon. Preferably, the silicon-based coating comprises a silane-based coating.
For the purposes of the present invention, "silane-based coating" refers to any coating comprising an organofunctional silane. Preferably, the silane-based coating has the following structural formula:
Y'-R'-SiX'3
wherein,
-SiX'3 comprises a first functional group;
-R' comprises a linking group;
-Y' comprises a second functional group.
The first functional group SiX'3 is capable of binding to an elongated metal element.
X' represents a silicon functional group independently selected from the group consisting of-OH, -R, -OR, -OC (= O) R and halogens such as-Cl, -Br, -F, wherein-R is an alkyl group, preferably C1-C4Alkyl, most preferably-CH3and-C2H5。
The second functional group Y' is capable of binding to or interacting with at least one functional group of the modified polyolefin. Preferably, Y' is selected from the group consisting of-NH2、-NHR'、-NR'2Unsaturated double or triple bond carbon-carbon end groups, acrylic groups, methacrylic groups and methyl or ethyl esters thereof, -CN, -SH, isocyanate groups, thiocyanate groups and epoxy groups.
According to the invention, "titanium-based coating" refers to any coating comprising titanium. Preferably, the titanium-based coating comprises a titanate.
According to the invention, by "zirconium-based coating" is meant any coating comprising zirconium. Preferably, the zirconium based coating comprises a zirconate.
The thickness of the first layer is preferably no more than 1 μm, more preferably the thickness of the first layer is in the range of 5nm to 1000nm, most preferably the thickness of the first layer is in the range of 5nm to 200 nm.
The second layer is applied over the first layer of elongated metal elements. It is used to improve the adhesion between the first layer and the thermoplastic matrix. To this end, the second layer comprises a modified polyolefin: a co-polyolefin or a grafted polyolefin. Also, the modified polyolefin is a polyolefin copolymerized or grafted with at least one monomer comprising an anhydride or carboxylic acid functional group. The second layer interacts well with the thermoplastic material in the matrix.
WO99/20682 describes that metal elements for reinforcing polymer products can be coated with a monolayer based on a bifunctional silane coupling agent to obtain good adhesion, and that the metal elements can be further coated with an unmodified polyolefin layer (i.e. polyethylene, polypropylene or polybutylene) on the monolayer. The adhesion between the metal element coated with aminosilane and unmodified polyolefin (i.e. unmodified polyethylene or unmodified polypropylene) and the polymer matrix is measured by the POF test. The POF test is used to measure the force with which a metal element is pulled from a polymer matrix. POF test results show that the adhesion between the metal element coated with aminosilane and unmodified polyolefin and the polymer matrix is very poor and the metal element is very easily pulled out of the matrix. According to the results of the adhesion test, the polyolefin layer, which in WO99/20682 is an unmodified polyolefin, does not bring about an additional adhesion effect with the polymer product for the metal element coated with a single layer. In other words, the adhesion of the metal member coated with a single layer and an unmodified polyolefin layer to the polymer product is similar to or even inferior to the adhesion of the metal member coated with a single layer to the polymer product. The unmodified polyolefin does not adhere to the silane.
The present invention improves the second layer from unmodified polyolefin to modified polyolefin compared to WO 99/20682. The copolymerized or grafted anhydride or carboxylic acid functional polyolefin layer brings about the advantage of good adhesion between the metal element coated with the adhesion-promoting layer and the polymer composite. The adhesion of the metal element coated with an adhesion promoting layer and a polyolefin layer of co-polymerized or grafted anhydride or carboxylic acid functional groups to a thermoplastic substrate is better than the adhesion promoting layer and the unmodified polyolefin layer. The modified polyolefin of the invention greatly improves the adhesion between the thermoplastic material in the promoter layer (e.g., a silicon-based coating, a titanium-based coating, or a zirconium-based coating) and the substrate. The two layers of promoter layer and polyolefin layer copolymerized or grafted with anhydride or carboxylic acid functional groups bring about improved adhesion between the elongated metal element and the thermoplastic material in the substrate.
Preferably, the anhydride comprises an anhydride. More preferably, the anhydride comprises maleic anhydride.
The carboxylic acid functional groups preferably comprise acrylic acid functional groups.
The thickness of the second layer is determined by the adhesion requirements between the first layer and the thermoplastic matrix. Preferably, the thickness of the second layer is in the range of 10 μm to 100 μm, more preferably, the thickness of the second layer is in the range of 30 μm to 50 μm.
According to the invention, the polyolefin is preferably selected from polyethylene or polypropylene.
Due to the two-layer coating it shows good adhesion between the elongated metal elements and the thermoplastic material matrix, so that the elongated metal elements are well embedded in the matrix.
For the purpose of the present invention, the elongated metal element may be a metal wire or a metal cord, such as a steel wire or a steel cord.
"wire" means a metal filament having any type of cross-section and any diameter. Preferably, the metal wire is a round or flat wire. Steel wires of different types are also conceivable.
For the purposes of the present invention, a "metal cord" is defined as a structure consisting of two or more bundles of filaments or threads or a combination of filaments and threads.
An example of a steel cord is a steel cord having the following structure: 1+6, 2+7, 3+9, 4+6, 3 × 1, 7 × 1 or 1+6+ 12.
"thread" is defined as a collection of filaments that are joined together to form a unit product for further processing.
The description of the structure follows the manufacturing sequence of the rope, i.e. starting from the inner most filament or thread and moving outwards. The complete description of the rope is given by:
（N×F）+（N×F）+（N×F）
where N = number of lines;
f = number of filaments.
(when N or F is equal to 1, they should not be included)
Any metal may be used to provide the elongated metal elements. Preferably, alloys are used, such as high carbon steel alloys, low carbon steel alloys or stainless steel alloys.
The elongated metal element may be uncoated or may be coated with a suitable coating prior to application of the first layer. Such a suitable coating may be a zinc or zinc alloy coating, such as a zinc brass coating, a zinc aluminium coating or a zinc aluminium magnesium coating. Such a coating may prevent corrosion of the elongated metal element by water or acid, while it may also improve adhesion between the elongated metal element and the first layer.
The polymer composite has good hardness and creep resistance due to the reinforcement of the elongated metal elements.
According to a particular embodiment of the invention, the reinforced polymer composite is mixed with wood particles. The wood particles in the reinforced polymer composite improve the E-modulus of the composite. The wood particles interact well with the thermoplastic material and the E-modulus of the composite material is therefore high. In addition, the wood particles provide a natural appearance to the final product, enabling it to be made to look like wood.
According to the present invention, the thermoplastic material is preferably a polymer selected from the group consisting of polyolefins, co-polyolefins, grafted polyolefins or combinations thereof. Preferably, the copolymerized or grafted polyolefin is a polyolefin copolymerized or grafted with at least one monomer comprising an anhydride or carboxylic acid functional group.
Preferably, the thermoplastic material is the same as the material of the second layer.
According to another aspect of the present invention, a method of manufacturing a reinforced polymer composite is provided.
The method comprises the following steps:
-providing at least one elongated metal element;
-applying a first layer on the elongated metal element, said first layer comprising an adhesion-promoting layer;
-applying a second layer on the first layer, said second layer comprising a polyolefin copolymerized or grafted with at least one monomer comprising an anhydride or a carboxylic acid functional group;
-embedding at least one elongated metal element coated with a first layer and a second layer in a matrix of thermoplastic material.
Preferably, the thermoplastic material matrix is mixed with wood particles before embedding the metal elements. The concentration of wood particles is 0wt% to 95 wt%.
The first and second layers may be applied by any technique known in the art.
Preferably, the first layer is applied by dipping the elongated metal element in an adhesion promoter bath. Subsequently, the coated elongated metal element may be dried.
Preferably, the second layer is applied on the first layer by applying molten polyolefin copolymerized or grafted with at least one monomer containing anhydride or carboxylic acid functional groups onto the elongated metal element through an extrusion die at high pressure or by coating a solution or emulsion of polyolefin copolymerized or grafted with at least one monomer containing anhydride or carboxylic acid functional groups on the elongated metal element followed by drying the coating.
And the method of making the reinforced polymer composite may comprise drying, curing, shaping and/or cutting to obtain the cross-sectional profile desired by the market or customer.
According to another object of the invention, an elongated metal element is provided for reinforcing a polymer composite. The elongated metal element is coated with at least a first layer comprising an adhesion promoting layer and a second layer comprising a polyolefin copolymerized or grafted with at least one monomer comprising an anhydride or carboxylic acid functional group.
The first layer comprises an adhesion promoting layer comprising a silicon-based coating, a titanium-based coating, or a zirconium-based coating.
The second layer comprises a polyolefin copolymerized with or grafted with at least one monomer comprising an anhydride or carboxylic acid functional group. Preferably, the polyolefin is polyethylene or polypropylene.
The elongated metal element may be uncoated or may be coated with a suitable coating prior to application of the first layer. Such a suitable coating may be a zinc or zinc alloy coating, such as a zinc brass coating, a zinc aluminium coating or a zinc aluminium magnesium coating. Such a coating may prevent corrosion of the elongated metal element by water or acid, while it may also improve adhesion between the elongated metal element and the first layer.
Due to the good adhesion between the elongated metal elements and the thermoplastic material matrix and the good reinforcement of the elongated metal elements, the reinforced polymer composite is strong and stable enough to be used in load bearing applications, particularly for homes, telephone poles, window and door frames, scaffold boards, shore reinforcements, and the like. Furthermore, the reinforced polymer composite is manufactured into a profile having a plurality of hollow sections, in particular having thin walls. The high stiffness of the polymer composite provides greater elastic stability of the load pressure and shear sections between the plurality of cavities.
"load bearing" refers to bearing weight and force.
The reinforced polymer composite may have the shape of an I-shape, an H-shape, or any other profile comprising a body and legs or arms in cross-section. In addition, the reinforced polymer composite may be in the form of a tubular profile, a plurality of tubular profiles, a hollow profile, or a plurality of hollows in cross-section.
In the present invention, "wt%" refers to weight percent, and the total weight is the weight of the reinforced polymer composite.
Brief description of the drawings
Figure 1 shows a cross-sectional view of a prior art round steel wire without any coating;
figure 2 shows a cross-sectional view of a round steel wire having a first layer and a second layer;
FIG. 3 shows a cross-sectional view of a flat wire having a first layer and a second layer;
figure 4 shows a cross-sectional view of a 7 x 1 steel cord with a first layer and a second layer;
figure 5 shows a cross-section of a 7 x 1 steel cord with a first layer;
FIG. 6 shows a cross-sectional view of a reinforced polymer composite I-profile;
figure 7 shows a cross-sectional view of a reinforced polymer composite tubular profile.
Detailed Description
The round steel wire is manufactured according to the following method:
the wire composition preferably has a carbon content in the range of a minimum carbon content of 0.60% and a maximum carbon content of about 1.10%, a magnesium content in the range of 0.40% to 0.70%, a silicon content in the range of 0.15% to 0.30%, a maximum sulfur content of 0.03%, a maximum phosphorus content of 0.30%, all percentages being weight percentages, wherein the total weight is the weight of the wire. Usually only traces of copper, nickel, aluminum, titanium, nitrogen and/or chromium are present except in order to obtain a very high tensile strength.
For removing oxides present on the surface, first of all by mechanical descaling and/or in H2SO4Or acid washed in HCl solution to clean the wire. The strands were then rinsed in water and dried. The dried strand is then subjected to a first series in order to reduce the diameter up to a first intermediate diameterAnd (4) dry stretching operation.
At this first intermediate diameter, for example between about 3.0 and 3.5mm, the dry drawn steel wire is subjected to a first intermediate heat treatment, called annealing. The steel wire is then ready for further mechanical deformation.
The steel wire is thereafter further dry drawn in a second diameter reduction step from the first intermediate diameter up to a second intermediate diameter. The second diameter is typically in the range of 1.0mm to 2.5 mm.
At the second intermediate diameter, the steel wire is subjected to a second annealing treatment to transform the steel wire into pearlite.
Alternatively, the steel wire may be coated with a zinc coating or a zinc alloy coating after the second annealing treatment.
The wire (with or without additional zinc or zinc alloy coating) is then subjected to a final series of cross-sectional reductions by means of a wet wire drawing machine to obtain a predetermined diameter.
Possibly the steel wire is an oil tempered steel wire.
It is possible to obtain flat wires or wires of other shapes, for example oval, I-shaped or H-shaped wires, from a round wire through one or more suitably shaped profile dies.
Several steel wires, round and/or flat, are possible, and the steel wire rope is obtained by a twisting machine.
Fig. 1 shows a round steel wire 10 known from the prior art without any coating.
Fig. 2 shows a steel wire 12 comprising a bare steel wire 10 and a first layer 14 and a second layer 16. First layer 14 comprises an aminosilane coating. The second layer 16 comprises a maleic anhydride grafted polypropylene coating.
The first layer 14 is applied to the steel wire 10 by dipping the steel wire rope in a solution comprising an aminosilane followed by drying. The second layer 16 is applied to the first layer 14 through an extrusion die at an elevated temperature with molten maleic anhydride grafted polypropylene.
Fig. 3 shows a flat wire 22 comprising a bare wire 20 and a first layer 26 and a second layer 28. The first layer 26 comprises an aminosilane coating. The second layer 28 comprises a maleic anhydride grafted polypropylene coating. The steel wire 20 is coated with a zinc coating 24 prior to application of the first coating 26.
The first layer 26 is applied on the zinc coating 24 by dipping the steel wire in a solution comprising an aminosilane followed by drying. The second layer 28 is applied to the first layer 26 through an extrusion die at an elevated temperature with molten maleic anhydride grafted polypropylene. It is also possible to dry the steel wire 22 after extrusion.
Fig. 4 shows a steel cord 32 of 7 x 1 construction comprising a bare steel cord 30 consisting of 7 steel filaments of 0.35mm diameter, a first layer 34 and a second layer 36. The first layer 34 comprises an aminosilane coating. The second layer 36 comprises a maleic anhydride grafted polypropylene coating.
The first layer 34 is applied to the bare steel cord 30 by dipping the cord in a solution comprising an aminosilane followed by drying. The second layer 36 is applied to the first layer 34 through an extrusion die at an elevated temperature with molten maleic anhydride grafted polypropylene.
Fig. 5 shows a prior art steel cord 40 of a 7 x 1 construction comprising a bare cord 30 and a first layer 34.
The first layer 34 is applied to the bare steel cord 30 by dipping the cord in a solution comprising an aminosilane followed by drying.
The reinforced polymer composite is then fabricated. A thermoplastic matrix, such as a polyolefin, a co-polyolefin, a grafted polyolefin, or a combination thereof, may be mixed with the wood particles. If added, the wood particles are added at a concentration in the range of 0wt% to 95wt%, for example at a concentration of greater than 35wt%, more specifically in the range of 70wt% to 80 wt%. The wood particles are preferably dried before incorporation into the matrix to a moisture content of less than 1% (where 1% is weight percent and the total weight is the weight of the wood particles). At least one of the elongated metal elements, e.g. steel wire 12, steel wire 22 or steel cord 32, comprising at least two layers is then embedded in the matrix. The matrix is then cooled to obtain the reinforced polymer composite. And the reinforced polymer composite may be formed into a desired shape and cut to a desired length according to transportation and customer requirements. A detailed description has been disclosed in WO 2004/03541.
The adhesion of the elongated metal elements and the polymer composite diameter was measured by measuring the pull-out force (POF). The length of the elongated metal elements embedded in the polymer composite (embedding length) was determined. The force required to pull the elongated metal element from the polymer composite was measured. The larger the value of POF, the better the adhesion.
The adhesion of the steel wire 12 coated with two layers and the prior art steel wire 10 to the reinforced polymer composite was compared. Table 1 summarizes the results.
TABLE 1
Elongated metal element Prior art steel wire 10 Steel wire 12
Embedded length (mm) 25 25
POF/(POF of prior art steel wire 10) 1 11.6
According to table 1, the pull-out force between the oiled two layer steel wire 12 and the polymer composite is increased considerably compared to the pull-out force between the prior art steel wire 10 and the polymer composite. In other words, the adhesion between the elongated metal element coated with the two layers and the polymer composite is better than the adhesion between the elongated metal element and the polymer composite without any coating.
The adhesion of the steel cord 32, the prior art steel cord 40, the prior art steel cord 30 and the prior art steel cord 70 coated with two layers to a reinforced polymer composite comprising polypropylene as thermoplastic material was compared. The prior art steel cord 70 is a steel cord coated with an aminosilane as a first layer and a polypropylene as a second layer. Table 2 summarizes the results.
TABLE 2
Figure BDA00001633258200101
From table 2 it is clear that by using a steel cord 32 according to the invention coated with two layers, the adhesion between the steel cord and the thermoplastic matrix is strongly improved. The adhesion between the thermoplastic material and the steel filaments is improved more than 20 times compared to the prior art steel cord 30 (steel cord without any coating).
The prior art steel cord 40, coated with a layer of (aminosilane), shows poor adhesion to thermoplastic materials. For the prior art steel cord 70, a steel cord with an aminosilane coating as the first layer and a polypropylene (unmodified polypropylene) coating as the second layer, the adhesion between the steel filaments and the thermoplastic material is very poor. The adhesion between the prior art steel cord 70 and the thermoplastic material is even worse than the adhesion between the prior art steel cord 40 and the thermoplastic material.
From table 2 it can be concluded that the aminosilane coating or the combination of the aminosilane coating and the unmodified polypropylene coating does not give adhesion or very poor adhesion between the steel cord and the thermoplastic material.
Furthermore, the surprisingly excellent adhesion between steel cords using aminosilane and modified polypropylene coatings according to the invention is evident in table 2.
The adhesion of steel cords having a 4 x 7 structure, which were not coated (cord a), coated with a layer of maleic anhydride grafted polypropylene (cord B) and coated with a first layer of aminosilane and a second layer of maleic anhydride grafted polypropylene (cord C), respectively, to a reinforced polymer composite comprising polypropylene as thermoplastic material was compared. The steel cords A, B and C consisted of galvanized steel filaments with a diameter of 0.10 mm. Table 3 summarizes the results.
TABLE 3
Elongated metal element Steel wire rope A Steel wire rope B Steel wire rope C
Embedded length (mm) 25 25 25
POF/(POF of steel wire rope A) 1 4.87 8.80
From table 3 it is clear that the first coating of aminosilane and the second coating of maleic anhydride grafted polypropylene provides the best adhesion between the steel cord and the polymer composite.
Table 1, table 2 and table 3 show that elongated metal elements comprising at least a first layer and a second layer show good adhesion to polymer composites. The adhesion of the metal member of the present invention to the thermoplastic substrate is better than the adhesion of a metal member having only an adhesion promoting layer, only a modified polyolefin or two layers having an adhesion promoting layer and an unmodified polyolefin layer. Such reinforced polymer composites are stable enough to be used in load bearing applications, particularly for homes, telephone poles, window and door frames, scaffold boards, shore reinforcements, and the like.
FIG. 6 shows a first embodiment of a reinforced polymer composite 50 having type I-in cross-section. The polymer composite 50 comprises a polypropylene matrix having a wood particle concentration of 40wt% and flat steel wires 22 embedded in the matrix. The moisture content of the wood particles was 0.8%. The upper flange 52 and the lower flange 54 are reinforced with flat wires 22.
Fig. 7 shows another embodiment of a reinforced polymer composite 60 having a tubular profile in cross-section. The polymer composite 60 comprises a polyethylene matrix having a wood particle concentration of 70wt% and steel cords 32 embedded in the matrix. The moisture content of the wood particles was 0.6%. The upper and lower walls are reinforced with flat wire ropes 32.

Claims (17)

1. A reinforced polymer composite comprising a thermoplastic material matrix, said matrix being reinforced with at least one elongated metal element, characterized in that said elongated metal element is coated with at least a first layer comprising an adhesion promoting layer and a second layer comprising a polyolefin copolymerized or grafted with at least one monomer comprising an anhydride or carboxylic acid functional group before being embedded in said matrix.
2. A reinforced polymer composite as claimed in claim 1, characterized in that the thermoplastic material matrix further comprises wood particles, the wood particles being present in a concentration of 0 to 95 wt%.
3. A reinforced polymer composite according to claim 1 or 2, characterized in that the anhydride comprises an acid anhydride.
4. A reinforced polymer composite according to claim 3, characterized in that the anhydride comprises maleic anhydride.
5. A reinforced polymer composite according to claim 1 or 2, characterized in that the carboxylic acid functional groups comprise acrylic acid functional groups.
6. The reinforced polymer composite of any one of claims 1 to 5, wherein the polyolefin is polyethylene or polypropylene.
7. The reinforced polymer composite of any one of claims 1 to 6, wherein the adhesion promoting layer comprises a silicon-based coating, a titanium-based coating, or a zirconium-based coating.
8. The reinforced polymer composite of claim 7, wherein the silicon-based coating comprises a silane-based coating.
9. The reinforced polymer composite of any one of claims 1 to 8, wherein the thermoplastic material is selected from the group consisting of polyolefins, co-polyolefins, grafted polyolefins, or combinations thereof.
10. A reinforced polymer composite as claimed in any one of claims 1 to 9, characterized in that the thermoplastic material is the same as the material of the second layer.
11. A reinforced polymer composite according to any one of claims 1 to 10, characterized in that said elongated metal elements comprise at least steel or steel cords.
12. The reinforced polymer composite of claim 11, wherein the steel wire is a flat wire.
13. A reinforced polymer composite according to claim 11 or 12, characterized in that said steel wire is an oil tempered steel wire.
14. The reinforced polymer composite of any one of claims 1 to 13, characterized in that the reinforced polymer composite has the shape of an I-profile, an H-profile, a tubular profile or a plurality of tubular profiles in cross-section.
15. A method of making a reinforced polymer composite comprising the steps of,
-providing at least one elongated metal element;
-applying a first layer on the elongated metal element, the first layer comprising an adhesion promoting layer;
-applying a second layer on the first layer, said second layer comprising a polyolefin copolymerized or grafted with at least one monomer comprising an anhydride or a carboxylic acid functional group;
-embedding at least one elongated metal element coated with said first layer and said second layer in a matrix of thermoplastic material.
16. The method of manufacturing a reinforced polymer composite according to claim 15, characterized in that the application of the second layer on the first layer is carried out by applying the molten polyolefin copolymerized or grafted with at least one monomer containing anhydride or carboxylic acid functional groups onto the elongated metal element through an extrusion die under high pressure or by coating a solution or emulsion of the polyolefin copolymerized or grafted with at least one monomer containing anhydride or carboxylic acid functional groups onto the elongated metal element followed by drying the coating.
17. An elongated metal element, characterized in that said elongated metal element is coated with at least a first layer comprising an adhesion promoting layer and a second layer comprising a polyolefin copolymerized or grafted with at least one monomer comprising an anhydride or a carboxylic acid functional group.
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